Carbon materials have shown great potential in solving environmental problems resulting from the pollution from oils or organic solvents. However, developing low-cost and high-performance carbon-based three-dimensional (3D) frameworks is still a great challenge and highly desired. Herein, monolithic macroporous carbon (MMC) materials have been synthesized through the pyrolysis of kapok wadding materials (ultralow-cost fibrous materials, those comprised of fibers with the highest hollow degree in nature). Owing to their unique and superior properties, such as tubular structure, light weight, high porosity, desirable flexibility, and strong thermal/mechanical stability, the MMC materials exhibit a high loading capacity for organic solvents and oils (87-273 times their own weight) and excellent recyclability. Coupled with the easy, economical, and environment-friendly synthesis process, MMC materials will be promising candidates for industrial application for removing organic pollutants. Hopefully, the MMC materials and the corresponding synthesis approach will be further applied to wider applications (e.g., energy storage, synthesis of composite materials, and so on).